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Патент USA US2109700

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Patented Mar. 1, 1938
2,109,700
UNITED STATES PATIENT OFFICE
2,109,700
METHOD OF PARTIAL OXIDATION OF
HYDROCARBONS
Joseph Hidy' James, Pittsburgh, Pa., assignor to.
Clarence P. 'Byrnes, Trustee
Application July 27, 1933,
Serial No. 682,466
N0 Drawing.
9 Claims.
In several patents, including Reissue Patent No.
18,522 of July 12, 1932, and several copending ‘ap
plications including Ser, No. 272,567, ?led Janu~
ary 22, 1919 now Patent #2085221 and Ser. No.
435,355, ?led January 6, 1921 now Patent #2054,
571, I have disclosed vapor-phase partial-oxida
tion of hydrocarbons at relatively high temper
atures; especially of the aliphatic or naphthenic
(Cl. 260-116)
in pressure. During this second step the liquid
treated is preferably well agitated, as for exam
ple, by means of the compressed air or other gas
containing free oxygen used in the partial oxida
tion.
type, such as present in mineral, shale oil and the
in oils from low temperature distillation of coal,
whether saturated or unsaturated; preferably in
the presence of a catalyst. Such methods have
the advantage of extremely rapid attack, a certain
percentage of conversion being obtained in time
shortening such second-step.
.
'
The second step consists of oxidizing the vapor
phase product with air, oxygen or a gas contain
ng it, at temperatures so low, especially underthe
pared with hours when carried out in ordinary superatmospheric pressures used, that for all
liquid phase partial oxidation of the same hydro
carbons.
~ oxidation, although the product treated is pref
erably agitated or ?nely divided during this step._
The complex condensed mixtures from such va
20 nor-phase process contain
Due to the “opening up” or preparatory action _
oxygen derivatives
' intervals of seconds or fractions thereof; as com
ranging from alcohols through aldehydes, alde
of the vapor phase oxidation step, the molecules
hyde alcohols, ketones, etc. to oxygenated or
of the product are susceptible to further attack,
ganic acids: and when petroleum fractions are
treated, these bodies are present in different mo
lecular weights. There also occurs some dehy
whether saturated or unsaturated, and objection
drogenation and thermal decomposition of higher
molecular weight bodies, especially of the oxy
genated bodies.
I
A
Some of the compounds thus formed have pe
culiar or objectionable odors and often color; and
some bodies present readily polymerize and resin
original oxygenated acids are in most cases con-2
verted into dibasic acids of good color and odor.
The liquid phase oxidation step may be carried
out by the batch system or continuously. In the _
ify, thus contaminating certain products such, following examples, I employed the batch system
for example, as soaps when made directly there
from. Such vapor phase processes may be and
using a pressure reaction bomb having at its top
have been carried out under subatmospheric, at
mospheric and superatmospheric pressures, and
with one or more catalytic contacts; and where
more than one contact was used, with addition of
more gas containing free oxygen vbetween such
catalytic contacts, and with and without steam, or
other diluent, such as flue gas. Such processes
have been usually carried out with temperatures
above that of vaporization of the oil fraction
treated and preferably between 225° C. and 500°
— C. and normally between 250° C. and 450° C.
I have discovered that objectionable features of
the products of vapor phase oxidation may be
overcome and at the same time further oxida
tion may be advantageously obtained by sub
J'ecting the condensed product thereof, particu
larly the oily product which is non-soluble or
sparingly soluble in water: to a liquid phase par
tial oxidation at a relatively lower temperature
I than that in the vapor phase treatment, and pref
erably at a considerable or high superatmospher
pressures. A two-stage air compressor was‘ con
nected by a high pressure tubing, having a back
seating check valve, to an air tube extending
down to near the bottom of the bomb within
about one-fourth inch thereof. This bomb was
immersed in a suitable liquid heating bath, petro
latum being generally used therefor and kept at
a substantially even desired temperature. The
capacity of the compressor at 200 \atmospheres
gauge pressure was 17 liters of air per minute;
and at 150 atmospheres was 8.5 liters per minute.
In the ?rst example, the material treated was
“wax distillate” treated by my vapor phase cata
lytic air process above referred to. The oily mix
ture produced had a saponi?cation number of 8.52
and contained approximately 27% of saponi?able '
material by volume.
With the compressor delivering air at the rate
of 17 liters per minute, 100 cc. of this total oily
mixture was treated for thirty minutes at ‘100
'
a
9,109,700
. pheres pressure inthje
" atmospheres-per sq. in. gauge pressure, at a tem
perature oi.’ 150° C.
~
step:
was ‘
made at 100 atmospheresig'augepressure and a
temperature 0! 125° .C.. The volume of oily ma
~
There resulted a recovery of about 96% of oily’ terial put inthengbomb was 100 cc. The result
‘ liquid of increased viscosity about the consisten-._ was 94% by volume'ci' an, oily. liquid of reddish
cy of glycerine, with about 31% by volume of orange color, having ‘some odor of acetic and
~ saponi?abie matter and a saponi?cation number butyric acids and no aldehyde odor. The sa
or 26.20 mg. KOH per gram. The odor was im- > poni?cation matter by volume was 40% and the
proved over that oi’ thematerial oxidized. There‘ saponi?cation number was 82.19 mg. KOH per
was little change in color.
-
.
These results show a marked increase in acid
10
gram.
content over that of the product of the ?rst step.
In the next or second test run, the ‘same raw
material was used, all conditions being the same
as in run ‘No. 1, except that the time was doubled.
In this case, the volume recovery was 94%. The
saponi?able matter by volume was 50%. The
product was an oily liquid somewhat more vis
acids from kerosene hydrocarbons. _'
_
'
treating the condensed‘ liquid oxidized product
resulting from relatively higher temperature oxi
'
In the third run, the effect or increasing the
air pressure was tried, in a run of one hour, the
air pressure being 150 atmospheres gauge pres
25
~
The advantages of my invention result from
acetic acid. The saponi?cation number was 61.47
mg. KOH per gram.
'
od is applicable to the production of organic
cous than ordinary engine oil and of a brown col
or. The odor was sweetish with some odor of
20
.,
This sixth run showed that the two-step meth
dation of hydrocarbons, such as vapor phase
treatment, by a lower temperature or “liquid
phase” oxidation. In this way, the speed oi! ob
taining the desired degree oi’ oxidation is much 20
increased over that'oi. liquid phase oxidation oi
hydrocarbons; while the disadvantages of vapor
phase treatment are reduced or largely over
come. The preparing or “opening up" action
of the ?rst higher temperature treatment greatly
sure per sq. in. The same raw material was used
and the same conditions, as in test No. 1, the
air passing up through the liquid at 8.5 liters
per minute. The result was a thick oily liquid
pouring slowly and of brown color. The odor was
sweetish with some odor of acetic and butyric
30
acids. The volume recovery was 90%, the sa
poni?able matter by volume 83%, and the sa
poni?cation number 105.4 mg. KOH per gram.
This test run showed the best conditions of ‘the
runs on the material used- and such conditions
35 vary according‘ to the > particular partly‘ oxi
dized material treated. When the same raw ma
terial was treated under the same conditions as
run No. 1, except that the bomb heating bath
was kept at 200° 0., there resulted a slow sooty
40 combustion of the oxidized mixture in the bomb.
In order to compare these above results-with
25
reduces the time, of the second or liquid phase
treatment. The mixture treated by the second
step contains various'oxygen, derivatives of dif
ferent degrees of oxidation, each class in differ
ent molecular weights, and usually unsaturated
bodies. In the second step, the further oxidation
is veffected at lower temperature, preferably in
liquid phase and further oxidation proceeds rap
idly as compared to. usual liquid phase oxidation
of straight hydrocarbons. The objectionable
characteristics of the oxidation product treated
35
are also improved. Substantially all oxygenated
-
material is carried over to acids and aldehydic
odors are removed as also those of unsaturated
bodies.
The acids produced in the ?rst step‘ may be
removed by saponi?oation or otherwise before
using the second step. The’ original hydrocar
those obtained by applying the second step di
rectly to straight hydrocarbons, I used in test
bon used may be cracked or uncracked. The
temperature and other factors may be varied
No. 4 the same conditions as in test No. 1, but ap-' in either or both steps, any pressure may be used
45 plied this second step to the original wax distil
in the ?rst step and the superatmospheric pres
late used in the vapor phase oxidation to obtain sure maybe varied in the second step.
the material treated in the preceding tests. The
result was a volume recovery of 97%. The prod
uct was of a light red color, substantially no odor,
50 saponi?cation No. 1.78 mg. KOH per gram, and
saponi?able matter by volume 8%. These re
sults show very slight attack on the straight hy
drocarbons of the fraction treated.
In another test, No. 5, I repeated test No. 4,
55 except that the temperature was kept at 200° C.
with a volume recovery of 97%, the resulting oily
‘mixture was of reddish color, the odor. slightly
acidic, apparently from organic acids of low mo
lecular weight, the saponi?cation matter by vol
60 ume 15% and the saponi?cation number 12.55
mg. KOH per gram. .
65
Tests Nos. 4 and 5 show the remarkable're
sults gained by applying a vapor phase catalytic
oxidation prior to air pressure oxidation in the
liquid phase.
The following runs show the application of my
plural step method to a kerosene:
' Run No. 6, I used-Venezuelan kerosene, which
had been subjected to my vapor phase catalytic
70 air oxidation. This material contained 23% of
saponi?able matter by volume and its saponi
?cation number was 16.38 mg. KOH per gram.
Since a preliminary run had shown that a tem
perature of 150° C. was too high at 100 atmos
The product of the ?rst step may be fractioned'
and a‘ fraction thereof treated by the second step.
The ?nal product may be fractioned prepara
tory to further treatment. The unoxidized por
tion or less oxidized portions may be removed
and retreated by either or both steps. The proc
ess may be applied to' aromatic or cyclic hydro
carbons. The raw material may be widely varied,
the second step may be carried out as a continu
ous one or by the batch system, and other
changes may be made, without departing from .
60
my invention.
I claim:
'
'
1. In the method of improving an oily portion
of condensed product of vapor phase oxidation
of aliphatic hydrocarbon, the step consisting of
subjecting said oily portion while in liquid phase
(i5
to the action of free oxygen while under pressure
on the order of at least 100 atmospheres.
2. In the method of improving an oily portion '
of condensed product or vapor phase oxidation
of aliphatic hydrocarbon,‘ the steps consisting of 70
removing acids, .and then subjecting the said
oily portion in liquid phase to- the action of free
oxygen while under pressure on the order of at
least 100 atmospheres.
3.- In the method of improving an oily portion q(5
2,109,100
3
of the condensed product of vapor phase enda
and agitating the same by supplying the said‘ gas
under pressm'e.
phase to free oxygen under pressure on the order
0! at least 100 atmospheres, and then fractioning
the product.
4. In the method of improving an oily portion
of the condensed product of vapor phase oxida
tion of mainly ‘ aliphatic hydrocarbon,
-
7. In the method of improving an oily-por
tion of the condensed product of vapor phase
oxidation of mainly aliphatic hydrocarbon, the
steps consisting of subjecting said oily portion in
liquid phase to a gas containing ‘free oxygen un
der pressure on the order of at least 100 atmos
pheres, agitating the same by supplying the said
gas‘ under pressure, and tapping o? excess pres
sure during the treating step.
“atmospheres.
5. In the method of improving an oily portion
or the condensed product of vapor phase oxida
gen under pressure on the order of at least 100
atmospheres, and supplying oxygen un'der pres
sure thereto in a continuous manner.
'
6. In the method of improving an oily portion
8. In the method of improving an oily portion
of the condensed product of vapor phase oxida
tion 01' mainly aliphatic hydrocarbon, the step
of subjecting said oily portion in liquid phase to
gas-containing free oxygen as
the sole reactive component while under pressure
on the order of at least 100 atmospheres.
9. In the partial oxidation of mainly aliphatic
hydrocarbons, the steps consisting of treating the
same in vapor or gaseous phase with a gas con
taining free oxygen at a relatively lower pres
sure' and a temperature of over 250° 0., and then
treating the same in liquid phase with free oxy
gen at a relatively higher pressure on the order
of at least 190 atmospheres.
'
JOSEPH HIDY JAMES;
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